CN1016168B - Insecticides and acaricides containing pyrazoline compounds - Google Patents

Abstract

The present invention describes the novel pyrazolines of general formula I, its preparation method and the application as insecticides with insecticidal and acaricidal effects. R ^{and R} in the formula I are the same or different, representing hydrogen or fluorine.

Description

The present invention relates to novel pyrazolines, their preparation and their use as insecticides.

A series of pyrazoline derivatives with insecticidal effects are known (for example: DOS 2304584 and 2529689 and EP 21506 and 113213).

Pyrazolines of the general formula are described in EP 21506:

wherein _R1 is especially a free phenyl group or a halogen-substituted phenyl group, _R2 is especially a haloalkoxy group having 1-6 carbon atoms, and X and Y are hydrogen or halogen. When R ₁ represents a phenyl group, the compounds referred to are two, wherein R ₁ is a free phenyl group and a p-chlorophenyl group, R ₂ represents trifluoromethoxy and X represents chlorine. When _R1 represents a halogen substituted phenyl, all disclosed compounds have the only X=chloro as a substituent in the 3rd position on the phenyl.

The object of the present invention was to provide pyrazolines with improved efficacy at better selectivity.

It has now been found that pyrazolines of general formula (I) have superior efficacy over known pyrazoline derivatives,

In the formula (I), R ¹ and R ² are the same or different and represent hydrogen or fluorine.

The present invention includes all isomeric forms of the compounds characterized by formula I and mixtures thereof.

The pyrazoline of general formula II:

React with an isocyanate of formula III

To prepare the compound of formula I of the present invention,

Prepared under the action of a solvent when necessary.

As the solvent, liquids inert to the reactants are preferably used, such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, which may be chlorinated if necessary, such as hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, di Chloromethane, chloroform, carbon tetrachloride, chlorinated ethylene, trichloroethylene and chlorobenzene; ethers such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, dioxane and tetrahydrofuran; Nitriles, such as acetonitrile, propionitrile and benzonitrile; Esters, such as ethyl acetate and amyl acetate; Amides, such as dimethylformamide, N-methylpyrrolidone or hexamethylphosphoric triamide; Sulfones and sulfoxides, Such as dimethylsulfoxide and sulfolane.

The above reaction can be carried out over a wide temperature range, usually between -20° and 100°C, preferably at room temperature.

This transformation is carried out at normal pressure, although it can also be carried out under elevated or reduced pressure.

The compounds prepared as described above can also be isolated from the reaction mixture according to customary methods, for example by distilling off the added solvent under normal or reduced pressure, by precipitation with water or by extraction, usually also by High purity is achieved by column chromatography purification or crystallization methods.

The pyrazolines according to the invention are colorless and odorless, in most cases crystalline compounds which are very poorly soluble in water and toluene and relatively easily soluble in ethyl acetate and dimethylformamide.

The pyrazolines of the formula II used as starting materials are known or can be prepared according to known methods.

The isocyanates of formula III used in the reaction process are known or can be prepared according to known methods.

The compounds of the present invention have an insecticidal and acaricidal action and are therefore suitable for controlling a wide variety of insects and mites, including veterinary ectoparasites. For example the so-called Lepidoptera such as diamondback moth, Spodoptera littoralis, cotton bollworm and cabbage butterfly (Pieris brassicae); Lucilia and Aedes aegypti (Aedes yellow fever); Homoptera including leaf aphids (Blattlausen) such as Megoura viciae and brown planthopper (Nilaparvata lugens); Coleoptera such as horseradish beetle (Phaedon cochleariae), cotton boll weevils (Anthonomus grandis) and squash beetles (Pyrophyllum genus, e.g. Cucumber 11-star beetles); Orthoptera such as German cockroaches (tea beetles); ticks such as B. Lice such as cattle lice (Damalinia bovis) and calf lice and spider mites (Spinnmilben) such as cotton spider mite and apple spider mite.

The compounds according to the invention are therefore excellently suitable for controlling insects and spider mites, in particular against harmful insects, and provide a valuable technical asset in this respect.

The compounds according to the invention can be used in a concentration of from 0.0005 to 5.0%, preferably from 0.001 to 0.1%, at which concentration the weight in grams of the biologically active substance contained in 100 ml of the preparation is known.

The compounds of the invention can be applied alone, mixed with each other, or together with other insecticidally active substances. If necessary, depending on the desired purpose, other plant protection agents, insecticides such as insecticides, acaricides or insecticides can be added. Fungal agent.

Increased intensity of action and speed of action can be achieved, for example, by active enhancing adjuvants such as organic solvents, wetting agents and oils. The addition of these adjuvants allows, if necessary, a reduction in the dose of the active substance.

Phospholipids can also be used as incorporation components, for example from the group consisting of phosphatidylcholines, hydrogenated phosphatidylcholines, phosphatidylethanolamines, N-acyl-phosphatidylethanolamines, phosphatidylinositols, phosphatidylserines, lysolecithins and compounds such as phosphatidylglycerol.

According to the purpose of use, the characteristic active substances or their mixtures can be formulated in the form of powders, sprays when adding liquid and/or solid substances or diluents and, if necessary, adhesives, wetting agents, emulsifiers and/or dispersing aids , particles, solutions, emulsions or suspensions.

Suitable liquid carrier substances are, for example, aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethylsulfoxide, dimethylformamide, furthermore mineral oil fractions and vegetable oils.

As solid carrier substances, minerals such as bentonite, silica gel, talc, kaolin, attapulgit, limestone and plant products such as flour are suitable appropriate.

In terms of surfactants, there are, for example, calcium lignosulfonate, polyvinyl alkylphenyl ether, naphthalenesulfonic acid and its salts, phenolsulfonic acid and its salts, formaldehyde condensates, fatty alcohol sulfates, and substituted benzenesulfonic acids and its salt.

The proportion of the active substance in the different formulations can vary within wide ranges, for example, containing about 10 to 90% by weight of active substance, about 90 to 10% by weight of liquid or solid carrier substance and optionally up to 20% by weight % of surfactants.

The insecticides can be applied conventionally, for example by spraying about 100 to 3000 liters per hectare with water as a carrier, and can also be applied in particulate form in so-called low-volume and ultra-low-volume methods.

To prepare the formulation, ingredients such as the following are added:

A. Powder spraying

20% by weight active substances

35% by weight white clay (Bleicherde)

8% by weight calcium lignosulfonate

2 wt% sodium N-methyl-N-oleoyl-taurate

35% by weight silicic acid

B. Ointment

45% by weight active substances

5% by weight sodium aluminum silicate

15% by weight cetyl polyglycol ether with 8 moles of ethylene oxide

2% by weight spindle oil

10% by weight polyethylene glycol

23 parts water

C. Emulsion concentrate

20% by weight active substances

75% by weight isophorone

5% by weight of a mixture based on nonylphenyl polyoxyethylene and calcium dodecylbenzenesulfonate

The following examples illustrate the preparation of compounds of the invention:

Example 1

3,4-bis(4-fluorophenyl)-4,5-dihydro-1-pyrazolecarbonic acid-(4-difluoromethoxyanilide)

Under stirring at room temperature, 7.03 g (0.038 mol) of 4-difluoromethoxyphenyl isocyanate was added to 9.85 g (0.038 mol) of 3,4-bis(4-fluorophenyl) in 80 ml of dichloromethane )-4,5-dihydropyrazole, and stirred at room temperature for 1 hour. The reaction mixture was filtered on silica gel and squeezed dry, the residue was treated with 100 ml of diisopropyl ether, the precipitated crystals were filtered off with suction and dried in vacuo (100 torr).

Yield: 14.7 g (87% of theory)

Melting point: 144°C

The following compounds, in which the substituents X, Y and Z are defined in formula I, were prepared in an analogous manner.

Example number R ¹ R ² Melting point °C

2 F F 135

3 H F 146

4 H H 140

The following practical examples demonstrate the biological activity of the compounds of the present invention:

Application example A

Therapeutic effect of treatments of faba beans against the black silkworm aphid [Schwarze Bohnenlaus (Aphis fabae Scop.)].

Make the seedling of broad bean grow to about 6 centimeters high in the greenhouse, one plant per pot. It is then covered with a substance that breeds black broad bean aphids. Then the plant is transplanted with 100-200 adults per tree, and the pot is sprayed and wetted with 0.1% of the corresponding active substance in the water preparation, and placed in a greenhouse at about 24°C, and it is killed after two days of investigation share of leaf aphids. Compared with the situation of untreated blank pots, the drug effect was calculated according to Abbott's method.

With the compounds according to the invention according to Examples 1 and 4, an effect of more than 75% is achieved.

Application example B

The role of preventive foliar treatments against rice brown planthopper.

In the greenhouse, the rice seedlings (15 plants per pot) are cultivated until the third leaf grows, and then the pots are sprayed with water preparation containing 0.1% of the active substance. After the spray layer is dry, each pot is covered with a Put about 30 brown planthoppers in each pot in a transparent cylinder, place them in a greenhouse at 26°C for two days, determine the proportion of dead planthoppers, compare with untreated blank pots, and calculate the effect according to the Abbott method The effect comes.

For the compounds according to the invention according to Examples 1-4, the effect is 75-100%.

Application example C

Killing effect on diamondback moth larvae.

The compound of the invention is used in a formulation containing 0.0064% of the active substance. For this, the acetone solution or milky concentrate of the compound of the invention can be diluted with water to the desired concentration before use. This preparation was sprayed on kohlrabi leaves (Brassica oleracea) in polystyrene Petri dishes at a dose of 4 mg per square centimeter, and after the spray layer was dry, Ten Plutella xylostella larvae were housed per dish and exposed to the treated feed in closed petri dishes for two days, followed by a single post-feeding on untreated kohlrabi leaves for another three days , the standard of effect evaluation is the percentage of larval mortality after 5 days.

The above tests show that the compounds of the present invention according to Examples 1-4 have an effect of 80-100%.

Application example D

Lethal effect on Egyptian cottonworm (Spodoptera littoralis) larvae (L2)

The compound of the present invention adds with containing 0.0064% effect substance, and to this, can use after diluting the acetone solution of the compound of the present invention or milky concentrate to required concentration with water, this preparation is to the small pinnate leaf pair of all capers (Vicia fabae) and 10 Egyptian cotton worm larvae (L2) were sprayed. In each test session, 4 mg of liquid medicine was sprayed per square centimeter in a polystyrene petri dish, and the closed petri dish was kept in the laboratory for They were kept under long-day conditions for 2 days, and then supplemented with a single supplementary feeding with untreated caper leaves on another 3 days. The criterion for evaluating the effect of the action was the mortality of the larvae after five days.

The above experiments show that the compounds of the present invention according to Examples 1-4 have an effect of 80-100% mortality.

Application example E

Contact effect on the larvae of Spodoptera americanum

The compound of the present invention is used as a preparation containing 0.0064% of the active substance. For this, the acetone solution or milky concentrate of the compound of the present invention can be diluted to the required concentration with water and used. Spray at a dose of 4 mg, and after the spray coat dries, 5 tobacco armyworms per petri dish are exposed to the spray coat for 24 hours, The larvae were then transferred to untreated petri dishes and fed a non-toxic prescribed diet for an additional four experimental periods, which were carried out under long-day conditions in the laboratory. The criterion for effect evaluation was the mortality of larvae after five days.

The above experiments show that the compounds of the present invention according to Examples 1-4 have an effect of 80-100% mortality.

Application example F

Soil deworming effect on corn rootworm/eggs (Diabrotica undecimpunctata)

The compound of the present invention is used with the preparation that contains 0.0064% action substance, and for this, can use after diluting the acetone solution of the compound of the present invention or milky concentrate to required concentration with water each time with 20 milliliters of such preparations and pour on plastic flower pots (66×66×82 mm), each of the flower pots is filled with 200 ml of soil, and each one is filled with about 100 corn rootworm eggs and 2 corns in the soil about 1 cm deep from the surface, and then, The pots were placed in the greenhouse under long-day conditions and 24-26°C for 14 days. The criterion for evaluating the effect was within 14 days in untreated pots with eggs and non-treated pots without eggs. growth of corn plants in.

The above tests show that the use of the compounds according to the invention according to Examples 1-4 does not interfere with the development of the plants.

Claims (4)

1, a kind of Insecticidal and acaricidal agent composition is characterized in that containing at least in the composition of said composition a kind of pyrazoline compounds as the logical formula I of active ingredient

(R in the formula ¹And R ²Identical or inequality, represent hydrogen or fluorine), and contain carrier substance and/or auxiliary material, wherein the content of active ingredient is 10-90% (weight), the content of liquid and/or solid carrier material is 90-10% (weight), at the tensio-active agent that can add 20% (weight) whenever necessary at most.

2, the Insecticidal and acaricidal agent method for compositions of preparation claim 1, this method comprises that the compound with at least a logical formula I mixes mutually with carrier substance and/or auxiliary material.

3, according to claim 2 preparation of compositions method, the preparation of its formula of (I) compound is the pyrazoline by logical formula II

(R in the formula ¹Definition and R in logical formula I ¹Definition identical),

Prepare with a kind of isocyanate reaction of formula III

(R in the formula ²Definition and R in logical formula I ²Definition identical),

And selectively use a kind of solvent.

4,, comprise said composition is applied to prevent and treat insect and spider mite (Spinnmilben) according to the purposes of claim 1 composition.